US3480084A - Composition and method using temporary soild diverting agent for aqueous fluids - Google Patents
Composition and method using temporary soild diverting agent for aqueous fluids Download PDFInfo
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- US3480084A US3480084A US715547A US3480084DA US3480084A US 3480084 A US3480084 A US 3480084A US 715547 A US715547 A US 715547A US 3480084D A US3480084D A US 3480084DA US 3480084 A US3480084 A US 3480084A
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- diverting agent
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- 239000000203 mixture Substances 0.000 title description 35
- 239000012530 fluid Substances 0.000 title description 20
- 238000000034 method Methods 0.000 title description 11
- 239000003795 chemical substances by application Substances 0.000 description 44
- 230000015572 biosynthetic process Effects 0.000 description 41
- 238000005755 formation reaction Methods 0.000 description 41
- 239000002245 particle Substances 0.000 description 15
- 235000013339 cereals Nutrition 0.000 description 14
- 239000003349 gelling agent Substances 0.000 description 14
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 12
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 12
- 239000007788 liquid Substances 0.000 description 9
- 240000006394 Sorghum bicolor Species 0.000 description 8
- 235000011684 Sorghum saccharatum Nutrition 0.000 description 8
- 235000009430 Thespesia populnea Nutrition 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 240000004713 Pisum sativum Species 0.000 description 7
- 235000010582 Pisum sativum Nutrition 0.000 description 7
- 240000008042 Zea mays Species 0.000 description 7
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 description 7
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 7
- 235000009973 maize Nutrition 0.000 description 7
- 239000002562 thickening agent Substances 0.000 description 7
- 244000303965 Cyamopsis psoralioides Species 0.000 description 6
- 235000019764 Soybean Meal Nutrition 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000004455 soybean meal Substances 0.000 description 6
- 208000005156 Dehydration Diseases 0.000 description 5
- 239000008365 aqueous carrier Substances 0.000 description 5
- 239000008135 aqueous vehicle Substances 0.000 description 5
- 235000012054 meals Nutrition 0.000 description 5
- 229920000569 Gum karaya Polymers 0.000 description 4
- 235000010494 karaya gum Nutrition 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 244000068988 Glycine max Species 0.000 description 3
- 235000010469 Glycine max Nutrition 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 3
- UBLAMKHIFZBBSS-UHFFFAOYSA-N 3-Methylbutyl pentanoate Chemical compound CCCCC(=O)OCCC(C)C UBLAMKHIFZBBSS-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- 241000512259 Ascophyllum nodosum Species 0.000 description 2
- 241000416162 Astragalus gummifer Species 0.000 description 2
- 241000206575 Chondrus crispus Species 0.000 description 2
- 229920002907 Guar gum Polymers 0.000 description 2
- 240000007472 Leucaena leucocephala Species 0.000 description 2
- 235000010643 Leucaena leucocephala Nutrition 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 229920001615 Tragacanth Polymers 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 235000013312 flour Nutrition 0.000 description 2
- 239000000665 guar gum Substances 0.000 description 2
- 235000010417 guar gum Nutrition 0.000 description 2
- 229960002154 guar gum Drugs 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229960002796 polystyrene sulfonate Drugs 0.000 description 2
- 239000011970 polystyrene sulfonate Substances 0.000 description 2
- 229920002102 polyvinyl toluene Polymers 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 230000000638 stimulation Effects 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 239000000375 suspending agent Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- 235000010487 tragacanth Nutrition 0.000 description 2
- 239000000196 tragacanth Substances 0.000 description 2
- 229940116362 tragacanth Drugs 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 241000934878 Sterculia Species 0.000 description 1
- 240000001058 Sterculia urens Species 0.000 description 1
- 235000015125 Sterculia urens Nutrition 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 244000098338 Triticum aestivum Species 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- -1 alkali metal salts Chemical class 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 210000004207 dermis Anatomy 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000000231 karaya gum Substances 0.000 description 1
- 229940039371 karaya gum Drugs 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920001206 natural gum Polymers 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229940006186 sodium polystyrene sulfonate Drugs 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/70—Compositions for forming crevices or fractures characterised by their form or by the form of their components, e.g. foams
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/66—Compositions based on water or polar solvents
- C09K8/68—Compositions based on water or polar solvents containing organic compounds
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/25—Methods for stimulating production
- E21B43/26—Methods for stimulating production by forming crevices or fractures
- E21B43/261—Separate steps of (1) cementing, plugging or consolidating and (2) fracturing or attacking the formation
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/26—Gel breakers other than bacteria or enzymes
Definitions
- a composition comprising: a material consisting substantially of whole and/or cracked natural grains or seeds, a particulated finely subdivided thickening agent, and an aqueous carrier or vehicle and the method of treating a subterranean formation penetrated by a wellbore which comprises injecting said composition down the wellbore and forcing at least some of it into the formation where such diverting agent serves as a temporary plugging agent to divert fluid to less accessible or tighter portions of the formation.
- Phthalic anhydride is also advantageously employed as an ingredient in the composition to aid in break down of the diverting agent, due to hydrolysis of the phthalic anhydride, thereby aiding in breaking the gel andsubsequent removal of diverting agent from the formation.
- fluid-loss control agents To alleviate this difliculty, one or more of a number of known fluid-loss control agents have been admixed with fluids injected into a geologic formation in attempts to divert the injected fluid from the more open and readily accessible portions of the formation to the tighter portions. Many of such fluid-loss control agents heretofore used, if effective as a diverting agent, have had a tendency to plug, more-or-less permanently, the channels into which they lodge.
- the principle object of this invention is to provide a temporary plugging agent to close off for a limited time the more open channels in the formation, i.e. while the agent is being injected, but which agent subsequent to injection softens rather rapidly and, in general disintegrates sufliciently to be readily pumpable and easily dislodged and removed from the formation.
- the invention is (A) a novel composition of matter comprising (1) an aqueous carrier liquid, (2) a pulverized natural or synthetic gum or resin or metal soap type thickening or suspending agent, of a particle size and possessing gelation properties to produce a viscosity in the liquid of at least about centipoises and preferably at least about 100 centipoises, and (3) a diverting agent of substantially whole or cracked.
- grains or seeds preferably having a relatively tough hull or dermis and a variation in particle size so that there is at least about 30 mesh sipes difference between the smallest and largest sizes present within an overall range of between about 3 and 325 mesh and (B) the method of treating a subterranean formation penetrated by a wellbore comprising injecting said composition down the wellbore and at least a portion thereof into the formation.
- phthalic anhydride is present as a fourth ingredient for the purpose of allowing the diverting agent to go into suspension, remain therein during injection, but which thereafter becomes completely hydrolyzed within a relatively short time, breaks the gel, and permits easy removal of the diverting agent from the formation.
- the thickening or gelling agent can be any one or more liquids or solids known to impart increased viscosity and suspending properties to an aqueous liquid.
- Pulverized natural gums are highly satisfactory, e.g. guar, soy bean, karaya, Irish moss, tragacanth, kelp, acacia, and the starchy and/or proteinaceous portions of natural grains and seeds which tend to form a colloidal suspension in water or aqueous solutions.
- Pulverized synthetic resins are also highly satisfactory, among which are polyvinyltoluene sulfonate, polystyrene sulfonate, acrylamide (both linear and cross-linked), and particularly alkali metal salts of the polymers.
- Metal soaps e.g. carboxylates of Na, K, or of other metals are satisfactory gelling or thickening agents, either alone or in admixture with the natural or synthetic resin, although the latter are preferred because of their more controllable, and quite acceptable gellation period.
- the particle size of the thickening agent should be such that at least about passes through a mesh screen and substantially all the balance passes through a 60 mesh screen.
- the selection and amount of gelling agent should be such as to increase the viscosity of the aqueous vehicle to at least about 10 centipoises and preferably to at least about 100 centipoises.
- the limit of the amount of gelling agent is merely one of practical limits, i.e. when the aqueous liquid tends to become too viscous it is unwise to use more.
- the diverting agent includes all sorts of natural grains and/or seeds and particularly comprises a mixture thereof, so long as there is a difference in the largest and smallest grains or seeds present.
- the seeds may be circular, flat, oblong, oval, or other shape so long as they remain in suspension, do not readily disintegrate or grow undesirably pulpy, or tend to form coalescent masses, and do remain substantially in suspenison during the well treating operation.
- the desirable range of sizes of diverting agent to use in the invention would be one wherein mesh sizes represent substantially equal numbers of particles all the way from 3 to 325 mesh.
- ranges of particle size of which about one-third by weight are of between 3 and 10 mesh, about one-third smaller than the openings in 10 mesh but larger than the openings in 25 mesh, and the remaining third smaller than the openings in 25 mesh but larger than the openings in 325 mesh are acceptable.
- the seeds or grains are preferably whole, but improved results are sometimes obtained when a portion thereof are cracked seeds or grains of the desired particle size. Processed grains or seeds (i.e.
- those having been treated chemically or mechanically are also acceptable so long as they are of proper size and the requirements of colloidal suspension and integrity or disis tough enough to retain its discreteness and to remain suspended during injection, but in its commercially available form often has a particle size range such that 75% or more is between 0.25 and .187 inch (i.e. varying between about 3 and 4 mesh) and the balance is of smaller size.
- Milo is likewise especially suitable to use with the peas because it also not only possesses all the requisite properties of the diverting agent but is commercially available, and often varies in particle size such that at least about 75% by weight are between 0.187 and 0.08 inch (i.e. between about 4 to 10 mesh), and the balance is of smaller size but larger than 325 mesh.
- the amount of diverting agent may be from about 1% by weight of the composition to the point of interference with pumpability, e.g. as much as 60%.
- the usual amount employed is between 6% and 30%.
- phthalic anhydride is helpful, first by replacing a portion of the grains by a completely water soluble agent, and secondly upon dissolution the phthalic anhydride hydrolyzes to phthalic acid. The gel and grain materials are thereby broken down by the acidic solution, thereby leading to easy removal of the diverting agent from the formation.
- the amount to use may be up to about 60% by weight of the total solids in the composition (diverting agents plus gelling agent), but usually is not more than 40% of the total solids in the formulation.
- the phthalic anhydride particle size is selected to replace an equivalent amount of similar particle size grain material so that the overall particle size distribution is not materially changed.
- the particle size is selected also to produce the desired rate of solubility of phthalic anhydride in aqueous solution. The larger the particles, the slower the rate of solution. Larger particle sizes, e.g. 10 to 40 mesh, are readily available and have satisfactory solubility rates in the temperature range of 125 to 250 F.
- the usual procedure followed to prepare the composition of the invention is to either (1) admix the gelling agent with the water, acid, or brine and thereafter admix the diverting agent therewith or (2) premix the gelling agent and diverting agent in substantially dry form and thereafter admix the resulting mixture with the 'water, acid, or brine.
- Sometimes a portion of the gelling agent is first admixed with the aqueous vehicle and thereafter an additional amount added with the diverting agent.
- the diverting agent may be admixed with the aqueous vehicle first but such procedure is less expedient. Phthalic anhydride, or other gel-breaking agent may be added at any time but is best added with the diverting agent.
- the usual procedure for treating a well is to admix some or all of the gelling agent with the aqueous liquid, either in a stationary or portable mixing tank or unit transfer or injection tubing or pipe and thereafter to admix the diverting agent and additional gelling agent if needed.
- the mixture is injected at sufficient pressure to force some of it into the formation (and to fracture if such is an objective) during which the diverting agent lodges in more accessible openings and diverts fluid being concurrently injected, or injected shortly thereafter, to less accessible portions of the formation.
- the diverting agent is sufficiently degenerated or solubilized to be removed by flushing or by producing fluids from the formation.
- Each of the above three mixes was suspended in an aqueous solution in amounts shown in Table I below, containing either 1% gum karaya or 1% guar gum as a thickening agent.
- the specimen so made was placed in a steel reservoir, provided at one end with a steel slotted opening one inch long. Slots of 0.25 inch and 0.15 inch width were available, thereby simulating openings in geologic formations.
- the other end of the pipe was capped, but had an opening provided for applying hydraulic pressure. Tests were conducted (at ambient temperature which was approximately 75 F.) until flow out through the slot was stopped. The pressure reading was then taken.
- aqueous composition of the invention is an excellent diverting and temporary plugging agent since the pressure rose very moderately after some of the agent had become lodged in the slot, as would occur if the agent had come up against and into fractures in a geologic formation.
- EXAMPLE 2 As an example ofthe emporary nature of the diverting plug, the following tests were made. Equipment similar to that used in Example 1 was used in these tests except that the reservoir was equipped at each end (beyond the previously mentioned openings) with valves which could be closed to maintain the reservoir and contents under pressure. It was also adapted with a heating jacket to reach and maintain a given temperature. Five hundred grams of solid diverting agent were prepared which contained Austrian peas, 20% whole milo maize, 30% rolled (crushed) milo maize, soy bean meal, and 25% soybean flour. This was added to 2000 mls.
- EXAMPLE 3 An old gas well in southern Texas was producing gas from the Edwards formation at the rate of approximately 0.5 million cu. ft. per day. This well was acidized using a diverting plug in water.
- the diverting plug contained 10 lbs. whole Austrian peas, lgs. Whole milo maize, 30 lbs. flake phthalic anhydride, 25 lbs. guar meal, 15 lbs. soy bean meal, 3 lbs. gum karaya and 1 lb. of a active sodium polystyrene sul'fonate in 4 barrels (168 gallons) of water.
- One thousand gallons of 28% hydrochloric acid were pumped down the tubing preceding the agent, the four barrels of diverting agent followed, and the final 1000 gallons of 28% inhibited hydrochloric acid were injected.
- the acid was flushed from the tubing and into the formation with water.
- the initial 1000 gallons of acid entered the formation at the rate of 5 barrels per minute at 2800 p.s.i. pressure. This pressure increased to 3900 p.s.i. as the diverting agent reached the formation and plugged existing channels.
- the final 1000 gallons of acid entered a new section of the formation at a reduced rate of about 2.5 barrels per minute at 3800 p.s.i. pressure. Gas production on the well increased from initial 0.5 to 2.5 million cubic feet per day following the treatment.
- aqueous HCl was then injected at 3800 p.s.i.g. for about 10 minutes at a rate of injection of about 2.5 barrels per minute. A total of 2000 gallons of acid was used during the complete treatment.
- an aqueous carrier liquid (2) a thickener or suspending agent selected from the class consisting of pulverulent guar gum, karaya gum, soy bean flour, Irish moss, tragacanth, kelp, acacia, starch, proteins, polystyrene sulfonate, polyvinyltoluene sulfonate, acrylamide, metal carboxylates, and mixtures thereof in an amount suflicient to increase the viscosity of the aqueous carrier liquid to at least about 10 centipoises, and (3) a diverting agent selected from the class consisting of substantially whole or cracked grains or seeds in an amount of between about 1.0% by weight of the-aqueous carrier liquid and that amount which renders the composition substantially unpumpable, and of a particle size such that there is a range in size between the smallest seeds and the largest of about 30 mesh sizes, and about by weight of the seeds are between 3 and 325 mesh.
- a thickener or suspending agent
- composition of claim 1 wherein there is present a gel-breaking agent.
- composition of claim 1 wherein said gel-breaking agent is phthalic anhydride in an amount of between about 1% and 40% of the combined weight of the gelling agent and diverting agent present.
- aqueous treating composition is an inhibited aqueous acid solution.
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Mining & Mineral Resources (AREA)
- Geology (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Geochemistry & Mineralogy (AREA)
- Environmental & Geological Engineering (AREA)
- Soil Conditioners And Soil-Stabilizing Materials (AREA)
Description
- States Patent Office 3,480,084 Patented Nov. 25, 1969 US. Cl. 166282 8 Claims ABSTRACT OF THE DISCLOSURE A composition comprising: a material consisting substantially of whole and/or cracked natural grains or seeds, a particulated finely subdivided thickening agent, and an aqueous carrier or vehicle and the method of treating a subterranean formation penetrated by a wellbore which comprises injecting said composition down the wellbore and forcing at least some of it into the formation where such diverting agent serves as a temporary plugging agent to divert fluid to less accessible or tighter portions of the formation. Phthalic anhydride is also advantageously employed as an ingredient in the composition to aid in break down of the diverting agent, due to hydrolysis of the phthalic anhydride, thereby aiding in breaking the gel andsubsequent removal of diverting agent from the formation.
In the treatment of a fluid-bearing subterranean formation penetrated by a wellbore, e.g. by injecting an acidizing or fracturing fluid into such formation to stimulate the flow of the natural fluid toward the wellbore, there is often a need for incorporating into such injected fluid an agent which temporarily inhibits too rapid dissipation of the injected fluid through existing channels, fissures, and the like in the formation. Unless inhibition of such rapid dissipation is eifectuated, very often the injected fluid takes courses in the formation wherein stimulation of production of natural formation fluids is least needed and often where such natural fluids have already been depleted. As a result, fluid following such courses of less resistance to flow is not available to be forced into the tighter portions of the formation where stimulation of the flow of natural fluids is most needed.
To alleviate this difliculty, one or more of a number of known fluid-loss control agents have been admixed with fluids injected into a geologic formation in attempts to divert the injected fluid from the more open and readily accessible portions of the formation to the tighter portions. Many of such fluid-loss control agents heretofore used, if effective as a diverting agent, have had a tendency to plug, more-or-less permanently, the channels into which they lodge.
The principle object of this invention is to provide a temporary plugging agent to close off for a limited time the more open channels in the formation, i.e. while the agent is being injected, but which agent subsequent to injection softens rather rapidly and, in general disintegrates sufliciently to be readily pumpable and easily dislodged and removed from the formation.
The invention is (A) a novel composition of matter comprising (1) an aqueous carrier liquid, (2) a pulverized natural or synthetic gum or resin or metal soap type thickening or suspending agent, of a particle size and possessing gelation properties to produce a viscosity in the liquid of at least about centipoises and preferably at least about 100 centipoises, and (3) a diverting agent of substantially whole or cracked. grains or seeds preferably having a relatively tough hull or dermis and a variation in particle size so that there is at least about 30 mesh sipes difference between the smallest and largest sizes present within an overall range of between about 3 and 325 mesh and (B) the method of treating a subterranean formation penetrated by a wellbore comprising injecting said composition down the wellbore and at least a portion thereof into the formation.
In a preferred embodiment of the invention, phthalic anhydride is present as a fourth ingredient for the purpose of allowing the diverting agent to go into suspension, remain therein during injection, but which thereafter becomes completely hydrolyzed within a relatively short time, breaks the gel, and permits easy removal of the diverting agent from the formation.
The thickening or gelling agent can be any one or more liquids or solids known to impart increased viscosity and suspending properties to an aqueous liquid. Pulverized natural gums are highly satisfactory, e.g. guar, soy bean, karaya, Irish moss, tragacanth, kelp, acacia, and the starchy and/or proteinaceous portions of natural grains and seeds which tend to form a colloidal suspension in water or aqueous solutions. Pulverized synthetic resins are also highly satisfactory, among which are polyvinyltoluene sulfonate, polystyrene sulfonate, acrylamide (both linear and cross-linked), and particularly alkali metal salts of the polymers. Metal soaps, e.g. carboxylates of Na, K, or of other metals are satisfactory gelling or thickening agents, either alone or in admixture with the natural or synthetic resin, although the latter are preferred because of their more controllable, and quite acceptable gellation period.
The particle size of the thickening agent should be such that at least about passes through a mesh screen and substantially all the balance passes through a 60 mesh screen.
The selection and amount of gelling agent should be such as to increase the viscosity of the aqueous vehicle to at least about 10 centipoises and preferably to at least about 100 centipoises. An amount of between about 0.1% and 5.0%, by weight of the aqueous vehicle, may be operable, but between about 0.5 and 2.0% is usually used. The limit of the amount of gelling agent is merely one of practical limits, i.e. when the aqueous liquid tends to become too viscous it is unwise to use more.
The diverting agent includes all sorts of natural grains and/or seeds and particularly comprises a mixture thereof, so long as there is a difference in the largest and smallest grains or seeds present.
The seeds may be circular, flat, oblong, oval, or other shape so long as they remain in suspension, do not readily disintegrate or grow undesirably pulpy, or tend to form coalescent masses, and do remain substantially in suspenison during the well treating operation. The wider the range of size of seeds or grains, between about 3 mesh and 325 mesh, the more effective is a given quantity of the diverting agent. The desirable range of sizes of diverting agent to use in the invention would be one wherein mesh sizes represent substantially equal numbers of particles all the way from 3 to 325 mesh. However, ranges of particle size of which about one-third by weight are of between 3 and 10 mesh, about one-third smaller than the openings in 10 mesh but larger than the openings in 25 mesh, and the remaining third smaller than the openings in 25 mesh but larger than the openings in 325 mesh are acceptable. The seeds or grains are preferably whole, but improved results are sometimes obtained when a portion thereof are cracked seeds or grains of the desired particle size. Processed grains or seeds (i.e. those having been treated chemically or mechanically) are also acceptable so long as they are of proper size and the requirements of colloidal suspension and integrity or disis tough enough to retain its discreteness and to remain suspended during injection, but in its commercially available form often has a particle size range such that 75% or more is between 0.25 and .187 inch (i.e. varying between about 3 and 4 mesh) and the balance is of smaller size.
Milo is likewise especially suitable to use with the peas because it also not only possesses all the requisite properties of the diverting agent but is commercially available, and often varies in particle size such that at least about 75% by weight are between 0.187 and 0.08 inch (i.e. between about 4 to 10 mesh), and the balance is of smaller size but larger than 325 mesh.
The amount of diverting agent may be from about 1% by weight of the composition to the point of interference with pumpability, e.g. as much as 60%. The usual amount employed is between 6% and 30%.
The use of phthalic anhydride is helpful, first by replacing a portion of the grains by a completely water soluble agent, and secondly upon dissolution the phthalic anhydride hydrolyzes to phthalic acid. The gel and grain materials are thereby broken down by the acidic solution, thereby leading to easy removal of the diverting agent from the formation.
The amount to use may be up to about 60% by weight of the total solids in the composition (diverting agents plus gelling agent), but usually is not more than 40% of the total solids in the formulation. The phthalic anhydride particle size is selected to replace an equivalent amount of similar particle size grain material so that the overall particle size distribution is not materially changed. The particle size is selected also to produce the desired rate of solubility of phthalic anhydride in aqueous solution. The larger the particles, the slower the rate of solution. Larger particle sizes, e.g. 10 to 40 mesh, are readily available and have satisfactory solubility rates in the temperature range of 125 to 250 F.
The usual procedure followed to prepare the composition of the invention is to either (1) admix the gelling agent with the water, acid, or brine and thereafter admix the diverting agent therewith or (2) premix the gelling agent and diverting agent in substantially dry form and thereafter admix the resulting mixture with the 'water, acid, or brine. Sometimes a portion of the gelling agent is first admixed with the aqueous vehicle and thereafter an additional amount added with the diverting agent. The diverting agent may be admixed with the aqueous vehicle first but such procedure is less expedient. Phthalic anhydride, or other gel-breaking agent may be added at any time but is best added with the diverting agent.
The usual procedure for treating a well is to admix some or all of the gelling agent with the aqueous liquid, either in a stationary or portable mixing tank or unit transfer or injection tubing or pipe and thereafter to admix the diverting agent and additional gelling agent if needed. The mixture is injected at sufficient pressure to force some of it into the formation (and to fracture if such is an objective) during which the diverting agent lodges in more accessible openings and diverts fluid being concurrently injected, or injected shortly thereafter, to less accessible portions of the formation. After from about one to about 12 hours (dependent in part on the pH and temperature conditions) the diverting agent is sufficiently degenerated or solubilized to be removed by flushing or by producing fluids from the formation.
4 EXAMPLE 1 The solids of the following recipes are illustrative of the composition of the invention:
Recipe A Parts Austrian peas 10-20 Milo maize 10-20' Phthalic anhydride 10-30 Soy bean meal 10-25 Guar meal 10-25 The larger sizes of the soy bean meal and guar meal act as diverting agents wherein the finer portion acts as a gelling agent. Any of a number of other wheat or cracked grains or seeds and/or of gelling agents other than soy bean meal or guar meal, of course may be used. The particular size of Austrian peas and milo maize supplement each other and are both admirably suited as to toughness when injected; but do subsequently thereafter degenerate and become as easily removed as desired.
The following mix A was prepared, in parts by weight:
Austrian peas 10 Milo maize 20 Phthalic anhydride 30 Soy bean meal 15 Guar meal 25 The mixture was passed through a series of sieves and gave the following results:
Retained on a: Mix A, percent 4 mesh sieve 9 10 mesh sieve 30 20 mesh sieve 27 40 mesh sieve 14 mesh sieve 14 Fines, passing through 100 mesh sieve 6 Other mixtures of diverting agents and gelling agent were prepared, but not according to the invention. The following results were obtained:
In the above mixes, some fines (small than 100 mesh sieve openings) were present in the Austrian peas and milo maize. This is not objectionable.
Tests on the three mixes, ,(A), (B), and (C) were conducted as follows:
Each of the above three mixes was suspended in an aqueous solution in amounts shown in Table I below, containing either 1% gum karaya or 1% guar gum as a thickening agent. The specimen so made was placed in a steel reservoir, provided at one end with a steel slotted opening one inch long. Slots of 0.25 inch and 0.15 inch width were available, thereby simulating openings in geologic formations. The other end of the pipe was capped, but had an opening provided for applying hydraulic pressure. Tests were conducted (at ambient temperature which was approximately 75 F.) until flow out through the slot was stopped. The pressure reading was then taken.
Grams of additive mix Confiegntration S1 t milling lfoss nleededhtofi Pressure gms. per 0 0 sum a ore r0 u Test No. Additive Mix 100 ml. in i iiehes shut ed p 06 S o 24 0. 15 200 48 2, 000 60 0. 15 170 104 2, 000 1. 2 0. 15 3, 500 42 2, 000 24 0. 25 700 168 600 24 0. 15 1, 200 288 2, 000 24 0. 15 350 84 2, 000
No test was continued above 2000 p.s.i.g. pressure in EXAMPLE 4 this series of tests.
Reference to Table I shows that the aqueous composition of the invention is an excellent diverting and temporary plugging agent since the pressure rose very moderately after some of the agent had become lodged in the slot, as would occur if the agent had come up against and into fractures in a geologic formation.
EXAMPLE 2 As an example ofthe emporary nature of the diverting plug, the following tests were made. Equipment similar to that used in Example 1 was used in these tests except that the reservoir was equipped at each end (beyond the previously mentioned openings) with valves which could be closed to maintain the reservoir and contents under pressure. It was also adapted with a heating jacket to reach and maintain a given temperature. Five hundred grams of solid diverting agent were prepared which contained Austrian peas, 20% whole milo maize, 30% rolled (crushed) milo maize, soy bean meal, and 25% soybean flour. This was added to 2000 mls. of tap water thickened with 1% gum karaya and 0.1% sodium polystyrene sulfonate (0.33% of a 30% active material.) This was heated to 200 F. and then maintained against the 0.15 inch slot at 500 p.s.i. for 1 hour. Approximately 270 mls. of fluid was lost in the first five minutes and an additional 80 mls. in the next 55 minutes. The test section was closed by use of the valves and heated for an additional 21 hours. The test had 50 p.s.i. residual pressure. After the forementioned time, the plug broke and the fluid flowed readily through the 0.15 inch slot under the 50 p.s.i. pressure. Similar tests were conducted for 3 and for 6 hours. A pressure of 400 p.s.i. was required to break the plug after 3 hours and 150 p.s.i. was required to break the plug after 6 hours. After 6. hours, the fluid and solids remaining in the reservoir were reversed out through a 0.1 inch slot at a pressure of 75 p.s.i. without pluging the slot.
EXAMPLE 3 An old gas well in southern Texas was producing gas from the Edwards formation at the rate of approximately 0.5 million cu. ft. per day. This well was acidized using a diverting plug in water. The diverting plug contained 10 lbs. whole Austrian peas, lgs. Whole milo maize, 30 lbs. flake phthalic anhydride, 25 lbs. guar meal, 15 lbs. soy bean meal, 3 lbs. gum karaya and 1 lb. of a active sodium polystyrene sul'fonate in 4 barrels (168 gallons) of water. One thousand gallons of 28% hydrochloric acid were pumped down the tubing preceding the agent, the four barrels of diverting agent followed, and the final 1000 gallons of 28% inhibited hydrochloric acid were injected. The acid was flushed from the tubing and into the formation with water. The initial 1000 gallons of acid entered the formation at the rate of 5 barrels per minute at 2800 p.s.i. pressure. This pressure increased to 3900 p.s.i. as the diverting agent reached the formation and plugged existing channels. The final 1000 gallons of acid entered a new section of the formation at a reduced rate of about 2.5 barrels per minute at 3800 p.s.i. pressure. Gas production on the well increased from initial 0.5 to 2.5 million cubic feet per day following the treatment.
This illustrates treatment of the Edwards formation in the San Miguel Creek gas field in Texas. The well was cored to a depth of 9948 feet with a 5 /2 inch casing and provided with a 2 /2 inch tubing to a depth of 9614 feet. A Baker 0 type packer was positioned in the annular space between tubing and easing at a depth of 9610 feet.
Water was first injected down the tubing at a rate of five 42-gallon barrels per minute at a maximum pressure of 2500 p.s.i.g. Inhibited aqueous 15% hydrochloric acid was then injected down the tubing at a rate varying between 25 barrels and 5 barrels per minute, the highest pressure (at the ground surface) which was reached was 2200 p.s.i.g. Four barrels of the aqueous fracturing fluid containing 100 pounds of the composition of the invention (which had been prepared according to Mix A above) was then injected. The pressure rose to 3900 p.s.i.g. in less than 5 minutes, thereby showing that the treatment according to the invention had plugged the larger fractures and channels in the formation being treated.
Additional inhibited 15% (by weight) aqueous HCl was then injected at 3800 p.s.i.g. for about 10 minutes at a rate of injection of about 2.5 barrels per minute. A total of 2000 gallons of acid was used during the complete treatment.
The well was allowed to stand for about two hours, during which time the ground level pressure on the injection line had subsided to 1900 p.s.i.g.
The well was then opened and put back into production. Gas production for the well showed definite improvement over that produced before treatment.
Having described my invention, what I claim and desire to protect by Letters Patent is:
1. A composition of matter effective for plugging cracks and crevices for a limited time when forced into such cracks and crevices comprising:
(1) an aqueous carrier liquid, (2) a thickener or suspending agent selected from the class consisting of pulverulent guar gum, karaya gum, soy bean flour, Irish moss, tragacanth, kelp, acacia, starch, proteins, polystyrene sulfonate, polyvinyltoluene sulfonate, acrylamide, metal carboxylates, and mixtures thereof in an amount suflicient to increase the viscosity of the aqueous carrier liquid to at least about 10 centipoises, and (3) a diverting agent selected from the class consisting of substantially whole or cracked grains or seeds in an amount of between about 1.0% by weight of the-aqueous carrier liquid and that amount which renders the composition substantially unpumpable, and of a particle size such that there is a range in size between the smallest seeds and the largest of about 30 mesh sizes, and about by weight of the seeds are between 3 and 325 mesh.
2. The composition of claim 1 wherein there is present a gel-breaking agent.
3. The composition of claim 1 wherein said gel-breaking agent is phthalic anhydride in an amount of between about 1% and 40% of the combined weight of the gelling agent and diverting agent present.
4. The method of treating a subterranean formation penetrated by a wellbore, wherein fluid-loss to the formation is excessive, employing an aqueous-base treating composition comprising injecting down the wellbore and into the formation the composition of claim 1.
5. The method according to claim 4 where the aqueous treating composition is an inhibited aqueous acid solution.
6. The method according to claim 4 wherein the treating composition is injected into the formation at a pressure sufiiciently high to fracture the formation.
7. The method of treating a subterranean formation penetrated by a wellbore, wherein fluid-loss to the formation is excessive, employing an aqueous-base treating composition comprising injecting down the wellbore and into the formation the composition of claim 2.
8. The method of treating a subterranean formation penetrated by a wellbore, wherein fluid-loss to the formation is excessive, employing an aqueous-base treating composition comprising injecting down the wellbore and into the formation the composition of claim 3.
, References Cited UNITED STATES PATENTS Boynton 175-72 Foster 252-85 Scott et a1 166--294 X Eberhard 2528.55
Foster et a1 2528.55 X
Hower et a1. 166292 Kuhn 166283 X STEPHEN J. NOVOSAD, Primary Examiner US. Cl.. X.R.
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US715547A Expired - Lifetime US3480084A (en) | 1968-03-25 | 1968-03-25 | Composition and method using temporary soild diverting agent for aqueous fluids |
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US3677343A (en) * | 1970-07-16 | 1972-07-18 | Union Oil Co | Method for improving the injection profile of a water injection well |
US3789927A (en) * | 1972-11-08 | 1974-02-05 | Dow Chemical Co | Treatment of gravel packed formations |
US3791838A (en) * | 1972-10-13 | 1974-02-12 | American Cyanamid Co | Vulcanization accelerator for natural and synthetic rubber |
US4068719A (en) * | 1975-12-24 | 1978-01-17 | Phillips Petroleum Company | Method for acidizing subterranean formations |
US4444264A (en) * | 1982-06-17 | 1984-04-24 | Halliburton Company | Method of using a diverting material for well treatment |
US6703013B1 (en) * | 1997-10-16 | 2004-03-09 | Sanwa Kagaku Kenkyusho Co., Ltd. | Polystyrene sulfonate-containing gel preparation |
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US9920610B2 (en) | 2012-06-26 | 2018-03-20 | Baker Hughes, A Ge Company, Llc | Method of using diverter and proppant mixture |
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US4444264A (en) * | 1982-06-17 | 1984-04-24 | Halliburton Company | Method of using a diverting material for well treatment |
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US6703013B1 (en) * | 1997-10-16 | 2004-03-09 | Sanwa Kagaku Kenkyusho Co., Ltd. | Polystyrene sulfonate-containing gel preparation |
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US10041327B2 (en) | 2012-06-26 | 2018-08-07 | Baker Hughes, A Ge Company, Llc | Diverting systems for use in low temperature well treatment operations |
US11486241B2 (en) * | 2012-06-26 | 2022-11-01 | Baker Hughes Holdings Llc | Method of using diverter and proppant mixture |
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US20180201827A1 (en) * | 2012-06-26 | 2018-07-19 | Baker Hughes, A Ge Company, Llc | Diverting systems for use in well treatment operations |
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US9938811B2 (en) | 2013-06-26 | 2018-04-10 | Baker Hughes, LLC | Method of enhancing fracture complexity using far-field divert systems |
US9994761B2 (en) | 2013-09-04 | 2018-06-12 | Halliburton Energy Services, Inc. | Hydrolyzable compounds for treatment of a subterranean formation and methods of using the same |
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US9995120B2 (en) | 2014-11-13 | 2018-06-12 | Saudi Arabian Oil Company | Flowing fracturing fluids to subterranean zones |
WO2016077135A1 (en) * | 2014-11-13 | 2016-05-19 | Saudi Arabian Oil Company | Flowing fracturing fluids to subterranean zones |
US10876045B2 (en) | 2015-11-16 | 2020-12-29 | Halliburton Energy Services, Inc. | Subterranean stimulation operations utilizing degradable pre-coated particulates |
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